CN105884569B - The method for preparing 1,2- dichloro hexafluoro cyclopentene - Google Patents
The method for preparing 1,2- dichloro hexafluoro cyclopentene Download PDFInfo
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- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/04—Thermal processes
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- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/202—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction
- C07C17/206—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms two or more compounds being involved in the reaction the other compound being HX
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- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/25—Preparation of halogenated hydrocarbons by splitting-off hydrogen halides from halogenated hydrocarbons
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/28—Molybdenum
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/22—Halogenating
- B01J37/26—Fluorinating
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- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
- C07C17/20—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms
- C07C17/21—Preparation of halogenated hydrocarbons by replacement by halogens of halogen atoms by other halogen atoms with simultaneous increase of the number of halogen atoms
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/22—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by depolymerisation to the original monomer, e.g. dicyclopentadiene to cyclopentadiene
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- C07C23/02—Monocyclic halogenated hydrocarbons
- C07C23/08—Monocyclic halogenated hydrocarbons with a five-membered ring
Abstract
1 is prepared the present invention relates to a kind of, the method of 2- dichloro hexafluoro cyclopentene, a kind of method preparing 1,2- dichloro hexafluoro cyclopentene, including following reaction step: (1), using cyclopentadiene as raw material, reacting to obtain tetrachloro pentamethylene with chlorine under liquid-phase condition；(2), using tetrachloro pentamethylene as raw material, under the conditions of existing for the fluorination catalyst, vapor phase chlorofluorination occurs with hydrogen fluoride and chlorine react to obtain 1,2- dichloro hexafluoro cyclopentene, the fluorination catalyst is chromium-based catalysts.Technical method provided by the invention, not only raw material is easy to get, fluorination catalyst activity is high and stability is high, and is suitable for large scale preparation 1,2- dichloro hexafluoro cyclopentene.
Description
Technical field
The present invention relates to a kind of methods for preparing 1,2- dichloro hexafluoro cyclopentene more particularly to one kind to pass through dicyclopentadiene
First heating is cracked into cyclopentadiene, then obtains tetrachloro pentamethylene through chlorination, finally carries out again with the gaseous mixture of hydrogen fluoride and chlorine
The method that 1,2- dichloro hexafluoro cyclopentene is prepared in gas phase catalytic reaction.
Background technique
1,2- dichloro hexafluoro cyclopentene is a kind of important intermediate, has a high industrial value, can prepare etching
Agent octafluoro cyclopentene, seven fluorine pentamethylene of cleaning agent 1,2,2,3,3,4,4- etc..
So far, many document reports 1, the preparation method of 2- dichloro hexafluoro cyclopentene.It is by chlordene ring penta 2 mostly
Alkene or octachlorocyclopentene are that starting material is synthesized, and the fluorination reagent used can be SbF5(see document US2459783 and
Ind.Eng.Chem.,1947,39(3),415–417.)、SbF3Cl2(see document J.Am.Chem.Soc., 1954,76 (2),
610–612.)、SbFxCl5-x(0 < x < 5) (see document J.Am.Chem.Soc., 1945,67,1235-1237.) or SbF3With
SbF3Cl2The mixture (see document Journal Indian Chem.Soc., 1953,30,525-528.) of composition, can also be
Anhydrous hydrogen fluoride.It must be in fluorination catalyst such as SbCl as fluorination reagent using anhydrous hydrogen fluoride5Catalyst is (see document
WO9743233, WO9600707 and US6218586) or bismuth-containing, iron catalyst (see document US5180861) under the conditions of carry out it is anti-
It answers.
Above-mentioned preparation process has the disadvantage in that starting material is difficult to obtain first, secondly, fluorination reagent be it is fluorine-containing and/
Or chlorine antimonial when, this kind of fluorination reagent highly corrosive, facile hydrolysis release hydrogen fluoride or hydrogen chloride gas, cause its
It is difficult to operate and control in use；Meanwhile when fluorination reagent is anhydrous hydrogen fluoride, the activity of fluorination catalyst is low, and is easy
Inactivation.
Summary of the invention
Technical problem to be solved by the present invention lies in the deficiencies solved in background technique, and it is easy to provide a kind of not only raw material
It obtains, fluorination catalyst activity is high and stability is high, suitable for the method for large scale preparation 1,2- dichloro hexafluoro cyclopentene.
A kind of method preparing 1,2- dichloro hexafluoro cyclopentene, including following reaction step:
(1), it using cyclopentadiene as raw material, reacts to obtain tetrachloro pentamethylene with chlorine under liquid-phase condition；
(2), using tetrachloro pentamethylene as raw material, under the conditions of existing for the fluorination catalyst, gas occurs with hydrogen fluoride and chlorine
The reaction of phase chlorofluorination obtains 1,2- dichloro hexafluoro cyclopentene.
The fluorination catalyst is chromium-based catalysts.
High-temperature roasting forms after the chromium-based catalysts are blended by chromium compound and metal powder, chromium compound and metal powder
Quality percentage composition be 95%~99.9%:0.1%~5%.
Wherein chromium compound is chrome green or chromium hydroxide, and metal powder is one of tungsten powder, molybdenum powder or several.
The high-temperature roasting condition are as follows: carry out roasting 6~15 hours in 300 DEG C~500 DEG C under nitrogen atmosphere.
For the chromium-based catalysts using preceding needing to be activated, described be activated is at 60 DEG C~450 DEG C in molar ratio
It is activated 6~15 hours in mixed gas for nitrogen and the HF composition of 10:1.
The molar ratio of the tetrachloro pentamethylene, hydrogen fluoride and chlorine be 1:5~20:5,0.1~1.5Ma of reaction pressure, instead
Answering temperature is 300 DEG C~500 DEG C, and time of contact is 2s~30s.
1~3:1 of molar ratio of the chlorine and cyclopentadiene, reaction temperature are 0~40 DEG C, reaction time 1-10h.
The preparation of the cyclopentadiene is using dicyclopentadiene as raw material, using nitrogen or other inert gases as dilution
Agent, heating cracking obtain cyclopentadiene.
The molar ratio of the diluent and dicyclopentadiene is 1:0.5~3,0.1~1.5Ma of reaction pressure, reaction temperature
It is 300 DEG C~450 DEG C, time of contact is 5s~30s.
Reaction condition of the present invention is preferred are as follows: the molar ratio of diluent and dicyclopentadiene is 1:1~2, reaction temperature 330
DEG C~370 DEG C, 0.1~1.5MPa of reaction pressure, time of contact is 10s~20s.
1~1.5:1 of molar ratio of the chlorine and cyclopentadiene, reaction temperature are 20~30 DEG C, reaction time 3-7h.
The molar ratio of the tetrachloro pentamethylene, hydrogen fluoride and chlorine be 1:10~15:5,0.1~1.5MPa of reaction pressure,
Reaction temperature is 370 DEG C~450 DEG C, and time of contact is 10s~20s.
Cyclopentadiene of the present invention is raw material, and cyclopentadiene Chang Yishuan copolymer form exists, when dicyclopentadiene heats
Decomposed is at cyclopentadiene, when being distilled under normal pressure, so that the temperature being fractionated on capital is maintained at 41~42 DEG C, Ji Kean
It is changed into cyclopentadiene entirely.It is preferred that using method of the invention.
Therefore using dicyclopentadiene as starting material, by gas phase Pintsch process, liquid phase chlorination and gas phase catalytic chlorofluorination
Reaction, obtains 1,2- dichloro hexafluoro cyclopentene, key reaction is as follows:
Type of reactor of the invention is not key, and tubular type can be used in the reactor that first step reaction and third step are reacted
Reactor, fluidized-bed reactor etc..In addition, adiabatic reactor or isothermal reactor also can be used, preferred tubular reactor.Second step
Reaction can carry out in the reactor of glass material, stainless steel material or polytetrafluoroethylene (PTFE) material, preferably glass autoclave.
The presoma for the chromium-based catalysts that the present invention uses is made of chromium compound and metal powder blending, quality percentage
Group becomes 95%~99.9%:0.1%~5%, and wherein chromium compound is chrome green or chromium hydroxide, preferably hydroxide
Chromium, metal powder are one of tungsten powder, molybdenum powder or several.The fluorination catalyst is prepared by the following procedure method and obtains: chromaking is closed
Object and metal powder are uniformly mixed by mass percentage, and compression moulding obtains catalyst precursor；Gained catalyst precursor,
Carry out roasting 6~15 hours in 300 DEG C~500 DEG C under nitrogen atmosphere, then at 60 DEG C~450 DEG C molar ratio be 1:10 HF with
It is activated 6~15 hours under the mixed gas atmosphere of nitrogen composition, fluorination catalyst is made.Other than above-mentioned fluorination catalyst,
He can also be used for the present invention by any of fluorination catalyst, such as: chromium oxide, charomic fluoride, fluorinated chromium oxide, aluminum fluoride,
Fluorinated aluminium oxide, the aluminum fluoride for being carried on active carbon, the chromium oxide on magnesium fluoride, containing various metals (such as Zn, Co, Ni,
Ge, In etc.) chromium oxide and activated carbon supported Antimony pentachloride or titanium tetrachloride etc..The fluorination catalyst of use is different, then instead
It answers condition different, including reaction temperature, reaction pressure, time of contact and molar ratio of material, leads to obtained 1,2- dichloro
Hexafluoro cyclopentene yield is also different.
The present invention prepares chromium-based catalysts using blending method, and chromium compound and metal powder are mixed system according to a certain percentage
Catalyst precursor is obtained, when catalyst precursor is through high-temperature roasting, chromium compound exists in the form of chromium oxide, and metal powder is then
Continuation exists with simple substance form, subsequently into the activation stage for the mixed gas being made of nitrogen and fluorine gas, is fluorinated in chromium oxide
It is charomic fluoride after the generation of no steam, the metal powders such as tungsten powder, molybdenum powder and indium powder and HF and chlorine react above-mentioned fluorination
Object is detached from catalyst structure in a manner of gas mostly, can not only provide duct for catalyst in this way, while increasing catalyst
Specific surface area and Kong Rong improve the activity of catalyst, and the metallic element not being lost is then mainly with simple substance or a small amount of hexafluoride
Form stay in the catalyst, the carbon distribution of catalyst when can effectively inhibit high temperature.Entire effect is seen, is prepared by above scheme
To fluorination catalyst not only use temperature high, and catalytic activity is high.
Advantages of the present invention: technical method provided by the invention, not only raw material is easy to get, fluorination catalyst activity is high and stablizes
Property it is high, and be suitable for large scale preparation 1,2- dichloro hexafluoro cyclopentene.
Specific embodiment
Analysis instrument: the glad chromatography GC-930 in Shanghai sea, hydrogen flame detector, chromatographic column are capillary column Al2O3/S“50m×
0.320mm × 0.25 μm " (manufacture of chromatographic technique research and development centre, Lanzhou Inst. of Chemical Physics, Chinese Academy of Sciences).
Gas chromatography analysis method: High Purity Nitrogen and hydrogen are used as carrier gas.Testing conditions are 250 DEG C of temperature of vaporization chamber, auxiliary
250 DEG C of 2 temperature of furnace, 250 DEG C of detector temperature, 40 DEG C of column furnace initial temperature is kept for 10 minutes, 15 DEG C/min of heating rate, eventually
230 DEG C of temperature is kept for 3 minutes.
Embodiment 1
1/2 inch of internal diameter, long 30cm the tubular reactor because of Kang Hejin in load 30 milliliters of inert aluminas, instead
It answers device to be warming up to 350 DEG C, is passed through nitrogen and dicyclopentadiene simultaneously in the reactor, control mole of nitrogen and dicyclopentadiene
Than for 1:1.5, time of contact is 15 seconds, reaction pressure 0.1MPa, reaction product is after 0 DEG C of ice bath is cooling, with gas-chromatography point
The composition for analysing organic matter, the results are shown in Table 1.
Embodiment 2
Operation same as Example 1 the results are shown in Table 1 except that reaction temperature is changed to 300 DEG C.
Embodiment 3
Operation same as Example 1 the results are shown in Table 1 except that reaction temperature is changed to 330 DEG C.
Embodiment 4
Operation same as Example 1 the results are shown in Table 1 except that reaction temperature is changed to 410 DEG C.
Embodiment 5
Operation same as Example 1 the results are shown in Table 1 except that reaction temperature is changed to 450 DEG C.
Embodiment 6
Operation same as Example 1 the results are shown in Table 1 except that time of contact is changed to 2s.
Embodiment 7
Operation same as Example 1 the results are shown in Table 1 except that time of contact is changed to 10s.
Embodiment 8
Operation same as Example 1 the results are shown in Table 1 except that time of contact is changed to 20s.
Embodiment 9
Operation same as Example 1 the results are shown in Table 1 except that time of contact is changed to 30s.
Embodiment 10
Operation same as Example 1, except that the molar ratio of nitrogen and dicyclopentadiene is changed to 1:0.5, as a result
It is shown in Table 1.
Embodiment 11
As a result operation same as Example 1 is shown in except that the molar ratio of nitrogen and dicyclopentadiene is changed to 1:1
Table 1.
Embodiment 12
As a result operation same as Example 1 is shown in except that the molar ratio of nitrogen and dicyclopentadiene is changed to 1:2
Table 1.
Embodiment 13
As a result operation same as Example 1 is shown in except that the molar ratio of nitrogen and dicyclopentadiene is changed to 1:3
Table 1.
Embodiment 14
Operation same as Example 1 the results are shown in Table 1 except that reaction pressure is changed to 0.5MPa.
Embodiment 15
Operation same as Example 1 the results are shown in Table 1 except that reaction pressure is changed to 1.0MPa.
Embodiment 16
Operation same as Example 1 the results are shown in Table 1 except that reaction pressure is changed to 1.5MPa.
Table 1
Embodiment 17
Cyclopentadiene and chlorine is added simultaneously in autoclave, the molar ratio for controlling cyclopentadiene and chlorine is 1:1.5, high
Pressing kettle temperature degree is 20 DEG C, reaction time 5h, and product is then dry with 4A molecular sieve through washing, alkali cleaning, and sampling carries out GC inspection
It surveys, experimental result is shown in Table 2.
Embodiment 18
Operation identical with embodiment 17 the results are shown in Table except that the molar ratio of cyclopentadiene and chlorine is changed to 1:1
2。
Embodiment 19
Operation identical with embodiment 17 the results are shown in Table except that the molar ratio of cyclopentadiene and chlorine is changed to 1:2
2。
Embodiment 20
Operation identical with embodiment 17 the results are shown in Table except that the molar ratio of cyclopentadiene and chlorine is changed to 1:3
2。
Embodiment 21
Operation identical with embodiment 17, except that reaction temperature is changed to 0 DEG C, the reaction time is changed to 10h, as a result sees
Table 2.
Embodiment 22
Operation identical with embodiment 17, except that reaction temperature is changed to 10 DEG C, the reaction time is changed to 7h, as a result sees
Table 2.
Embodiment 23
Operation identical with embodiment 17, except that reaction temperature is changed to 30 DEG C, the reaction time is changed to 3h, as a result sees
Table 2.
Embodiment 24
Operation identical with embodiment 17, except that reaction temperature is changed to 40 DEG C, the reaction time is changed to 1h, as a result sees
Table 2.
Table 2
Be related in embodiment 25~28 chromium-based catalysts the preparation method is as follows:
Chromic nitrate is dissolved in water, in 60 DEG C of addition ammonium hydroxide, controls between 7.5~8.5 range of pH value of solution, is stirring it
It is sufficiently precipitated under the conditions of mixing, by the slurry by filtration of formation, is washed with deionized to neutrality, is then dried 12 hours at 150 DEG C,
Obtain chromium hydroxide.
It according to quality percentage composition is 95% by gained chromium hydroxide and metal powder (metal powder be tungsten powder, molybdenum powder and indium powder)
~99.9%:0.1%~5% carries out uniformly mixed, compression moulding, obtains catalyst precursor, then by catalyst precursor
It carries out after roasting 10 hours for 450 DEG C under nitrogen atmosphere, the HF and nitrogen for being 1:10 with molar ratio at 60-450 DEG C form mixed
Activation 12 hours under atmosphere are closed, chromium-based catalysts are made.
Embodiment 25
1/2 inch of internal diameter, long 30cm the tubular reactor because of Kang Hejin in load 10 milliliters of chromium-based catalysts, should
Chromium-based catalysts presoma is to be mixed, suppressed according to quality percentage composition 97%:3% by chromium hydroxide and tungsten powder, is activated
Temperature is 300 DEG C.Reactor is warming up to 370 DEG C, while being passed through anhydrous hydrogen fluoride, tetrachloro pentamethylene and chlorine, controls anhydrous fluorine
The molar ratio for changing hydrogen, tetrachloro pentamethylene and chlorine is 12:1:5, and time of contact is 15 seconds, reaction pressure 0.1MPa, reacts 20h
Afterwards, reaction product is through washing, alkali cleaning, isolated organic matter, after drying, water removal, with the group of gas chromatographic analysis organic matter
At the results are shown in Table 3.
Embodiment 26
Operation identical with embodiment 25, except that chromium-based catalysts presoma be by chromium hydroxide and indium powder according to
Quality percentage composition 97%:3% is mixed, is suppressed, and reaction temperature is changed to 300 DEG C, the results are shown in Table 3.
Embodiment 27
Operation identical with embodiment 25, except that chromium-based catalysts presoma be by chromium hydroxide and tungsten powder according to
Quality percentage composition 99.9%:0.1% is mixed, is suppressed, and reaction temperature is changed to 330 DEG C, the results are shown in Table 3.
Embodiment 28
Operation identical with embodiment 25, except that the tungsten powder in chromium-based catalysts presoma is changed to molybdenum powder, it is living
Change temperature and be changed to 60 DEG C, and reaction temperature is changed to 410 DEG C, the results are shown in Table 3.
Table 3
Claims (8)
1. a kind of method for preparing 1,2- dichloro hexafluoro cyclopentene, including following reaction step:
(1), using cyclopentadiene as raw material, react with chlorine to obtain tetrachloro pentamethylene under liquid-phase condition, the chlorine with
1~3:1 of molar ratio of cyclopentadiene, reaction temperature are 0~40 DEG C, reaction time 1-10h；
(2), using tetrachloro pentamethylene as raw material, under the conditions of existing for the fluorination catalyst, gas phase chlorine occurs with hydrogen fluoride and chlorine
Fluorination reaction and obtain 1,2- dichloro hexafluoro cyclopentene, the molar ratio of the tetrachloro pentamethylene, hydrogen fluoride and chlorine be 1:5~
20:5,0.1~1.5MPa of reaction pressure, reaction temperature are 300 DEG C~500 DEG C, and time of contact is 2s~30s；
The fluorination catalyst is chromium-based catalysts；High-temperature roasting after the chromium-based catalysts are blended by chromium compound and metal powder
It forms, the quality percentage composition of chromium compound and metal powder is 95%~99.9%:0.1%~5%；Wherein chromium compound is
Chrome green or chromium hydroxide, metal powder are one of tungsten powder, molybdenum powder or several.
2. according to the method described in claim 1, the high-temperature roasting condition are as follows: under nitrogen atmosphere in 300 DEG C~500 DEG C into
Row roasting 6~15 hours.
3. according to the method described in claim 1, the chromium-based catalysts are using preceding needing to be activated, it is described be activated in
It is activated 6~15 hours in the mixed gas of nitrogen and HF composition that molar ratio is 10:1 at 60 DEG C~450 DEG C.
4. according to the method described in claim 1, the preparation of the cyclopentadiene be using dicyclopentadiene as raw material, with nitrogen or
Other inert gases obtain cyclopentadiene as diluent, heating cracking.
5. according to the method described in claim 4, the molar ratio of the diluent and dicyclopentadiene is 1:0.5~3, reaction pressure
0.1~1.5MPa of power, reaction temperature are 300 DEG C~450 DEG C, and time of contact is 5s~30s.
6. according to the method described in claim 5, the molar ratio of the diluent and dicyclopentadiene is 1:1~2, reaction temperature
It is 330 DEG C~370 DEG C, 0.1~1.5MPa of reaction pressure, time of contact is 10s~20s.
7. according to the method described in claim 1,1~1.5:1 of molar ratio of the chlorine and cyclopentadiene, reaction temperature 20
~30 DEG C, reaction time 3-7h.
8. according to the method described in claim 1, the molar ratio of the tetrachloro pentamethylene, hydrogen fluoride and chlorine is 1:10~15:
5,0.1~1.5MPa of reaction pressure, reaction temperature are 370 DEG C~450 DEG C, and time of contact is 10s~20s.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610256358.XA CN105884569B (en) | 2016-04-22 | 2016-04-22 | The method for preparing 1,2- dichloro hexafluoro cyclopentene |
| PCT/CN2016/086825 WO2017181517A1 (en) | 2016-04-22 | 2016-06-23 | Manufacturing method of 1,2-dichlorohexafluorocyclopentene |
| US16/094,263 US10538467B2 (en) | 2016-04-22 | 2016-08-19 | Manufacturing method of 1,2-dichlorohexafluorocyclopentene |
| KR1020187032808A KR102591316B1 (en) | 2016-04-22 | 2016-08-19 | Method for producing 1,2-dichlorohexafluorocyclopentene |
| JP2019505102A JP6621564B2 (en) | 2016-04-22 | 2016-08-19 | Process for preparing 1,2-dichlorohexafluorocyclopentene |
| EP16899153.7A EP3447042B1 (en) | 2016-04-22 | 2016-08-19 | Manufacturing method of 1,2-dichlorohexafluorocyclopentene |
| CN201680084576.8A CN109071385B (en) | 2016-04-22 | 2016-08-19 | Process for preparing 1, 2-dichlorohexachlorocyclopentene |
| PCT/CN2016/095975 WO2017181566A1 (en) | 2016-04-22 | 2016-08-19 | Manufacturing method of 1,2-dichlorohexafluorocyclopentene |
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| CN201610256358.XA CN105884569B (en) | 2016-04-22 | 2016-04-22 | The method for preparing 1,2- dichloro hexafluoro cyclopentene |
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| CN201680084576.8A Active CN109071385B (en) | 2016-04-22 | 2016-08-19 | Process for preparing 1, 2-dichlorohexachlorocyclopentene |
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| US20220115642A1 (en) | 2018-11-08 | 2022-04-14 | Lg Chem, Ltd. | Positive electrode active material for lithium rechargeable battery, manufacturing method therefor and lithium rechargeable battery comprising same |
| CN111072448B (en) * | 2019-10-31 | 2020-12-25 | 中国矿业大学(北京) | Method for synthesizing high-purity hexafluoro-1, 3-butadiene |
| CN112645792A (en) * | 2020-12-09 | 2021-04-13 | 中船重工（邯郸）派瑞特种气体有限公司 | Preparation method of octafluorocyclopentene |
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| JPS5163151A (en) | 1974-09-26 | 1976-06-01 | Shell Int Research | Jishikurobentajenno kisobunkaihoho |
| CA1120501A (en) | 1977-07-05 | 1982-03-23 | Arun C. Bose | Process for the production of hexachlorocyclopentadiene |
| IT1251951B (en) * | 1991-10-18 | 1995-05-27 | Ausimont Spa | PROCEDURE FOR PURIFYING 1,1,1-TRIFLUORO-, 2,2 DICHLOROETHANE FROM THE ISOMER 1,1,2-TRIFLUORO-1,2-DICHLOROETANO. |
| JPH07242595A (en) * | 1994-03-03 | 1995-09-19 | Chikara Kaneko | Production of alpha-fluorocycloalkenones |
| US6218586B1 (en) * | 1998-11-05 | 2001-04-17 | Central Glass Company, Limited | Method for preparing perhalogenated five-membered cyclic compound |
| JP4333894B2 (en) * | 2001-02-13 | 2009-09-16 | 日本ゼオン株式会社 | Method for producing perhalogenated 5-membered ring compound |
| JP4484572B2 (en) * | 2003-08-21 | 2010-06-16 | 昭和電工株式会社 | Method for producing hexafluoroethane and use thereof |
| TW200536812A (en) * | 2004-03-29 | 2005-11-16 | Showa Denko Kk | Process for production of 1,1,1,2-tetrafluoroethane and/or pentafluoroethane and applications of the same |
| CN100372607C (en) * | 2004-12-23 | 2008-03-05 | 西安近代化学研究所 | Florination catalyst, its manufacturing method and use |
| KR101127293B1 (en) * | 2007-03-30 | 2012-03-29 | 쇼와 덴코 가부시키가이샤 | Method for production of chlorinated and fluorinated compound |
| CN101306980B (en) * | 2008-06-30 | 2011-05-11 | 江苏安邦电化有限公司 | Method for preparing perchloro cyclopentadiene |
| CN101613248B (en) * | 2009-07-16 | 2012-09-05 | 浙江新和成股份有限公司 | Method for preparing cyclopentadiene by thermaldepolymerization of dicyclopentadiene |
| CN103570490B (en) * | 2012-07-21 | 2015-05-27 | 北京宇极科技发展有限公司 | Method for gas-phase synthesis for 1,2-dichloro-3,3,4,4,5,5-hexachlorocyclopentene |
| CN104907063A (en) * | 2014-03-12 | 2015-09-16 | 北京宇极科技发展有限公司 | Chromium base catalyst, and preparation method and use thereof |
| CN105884569B (en) * | 2016-04-22 | 2019-03-12 | 北京宇极科技发展有限公司 | The method for preparing 1,2- dichloro hexafluoro cyclopentene |
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